The Regiochemical Influence of Oxo-Substitution in Palladium-Mediated Hydrostannations of 1-Alkynes

Abstract

A systematic study of hydroxyalkynes and their derivatives showed that the presence and position of the oxygen functionality can influence the regioselectivity of their Pd(0)-catalyzed and free radical hydrostannations. Regioselectivity is influenced by functional group proximity, sterics, and the nature of the substituent (hydroxyl, ether, or ester). Information provided herein may be useful when deciding which methodology and/or protective group strategy to employ when forming vinylstannanes.

Keywords

alkynes - hydrostannations - neighboring-group effects - palladium - regioselectivity

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14

1-Alkynes containing four carbons or less proved too volatile to study under our reaction conditions.

16

Unless otherwise indicated, all starting materials are articles of commerce.

17

Hydrostannation of 3-butyn-1-ol (6) with 2 mol% Pd(Ph₃P)₄ affords a 44:50 mixture of 5A:5B, see reference 8k.

22

Interestingly, Pancrazi [4b] reported that Pd(0)-mediated hydrostannation of the TBS ethers of cis- and trans-3-methyl-2-penten-4-yn-1-ol to be highly selective for the proximal vinylstannanes.

32

The isolation of 20, 22, and 24 was complicated by their boiling points being similar to that of the solvent. Preparative-GC provided adequate amounts of the desired methyl ethers for this study.